Surfactants for agricultural products

ABSTRACT

Agricultural products, such as pesticides, plant growth regulators, fungicides, herbicides, and insecticides, may be formulated to include one or more surfactants, from one or more surfactant classes, such as siloxane derivatives of amino acids that have surface-active properties.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application No.62/950,391, filed Dec. 19, 2019, the disclosure of which is hereinincorporated by reference in its entirety.

FIELD

The present disclosure pertains to surfactants for use in agriculturalproducts. Such surfactants may include siloxane derivatives of aminoacids wherein the siloxane derivatives have surface-active properties.

BACKGROUND

Surfactants (molecules with surface-active properties) are widely usedin commercial agricultural formulations. These formulations may includea variety of active agricultural agents, such as pesticides, plantgrowth regulators, fungicides, herbicides, and insecticides. Many suchactive agricultural agents display limited water solubility or may beprone to crystallization. Precipitation of the active agricultural agentmay result in a loss of efficiency. Should the active agent beconcentrated in the precipitates, it is prevented from being evenlydistributed when sprayed on a field. Thus, surfactants may be includedin formulations to improve solubility, wetting, and spreadability of theactive agent.

The surfactants may be uncharged, zwitterionic, cationic, or anionic.Although in principle any surfactant class (e.g., cationic, anionic,nonionic, amphoteric) is suitable, it is possible that a formulation mayinclude a combination of two or more surfactants from two or moresurfactant classes.

Often, surfactants are amphiphilic molecules with a relativelywater-insoluble hydrophobic “tail” group and a relatively water-solublehydrophilic “head” group. These compounds may adsorb at an interface,such as an interface between two liquids, a liquid and a gas, or aliquid and a solid. In systems comprising relatively polar andrelatively non-polar components the hydrophobic tail preferentiallyinteracts with the relatively non-polar component(s) while thehydrophilic head preferentially interacts with the relatively polarcomponent(s). In the case of an interface between water and oil, thehydrophilic head group preferentially extends into the water, while thehydrophobic tail preferentially extends into the oil. When added to awater-gas interface, the hydrophilic head group preferentially extendsinto the water, while the hydrophobic tail preferentially extends intothe gas. The presence of the surfactant disrupts at least some of theintermolecular interaction between the water molecules, replacing atleast some of the interactions between water molecules with generallyweaker interactions between at least some of the water molecules and thesurfactant. This results in lowered surface tension and can also serveto stabilize the interface.

At sufficiently high concentrations, surfactants may form aggregateswhich serve to limit the exposure of the hydrophobic tail to the polarsolvent. One such aggregate is a micelle. In a typical micelle themolecules are arranged in a sphere with the hydrophobic tails of thesurfactant(s) preferentially located inside the sphere and thehydrophilic heads of the surfactant(s) preferentially located on theoutside of the micelle where the heads preferentially interact with themore polar solvent. The effect that a given compound has on surfacetension and the concentration at which it forms micelles may serve asdefining characteristics for a surfactant.

SUMMARY

The present disclosure provides formulations of agricultural products,such as pesticides, plant growth regulators, fungicides, herbicides, andinsecticides. These products may be formulated to include one or moresurfactants from one or more surfactant classes disclosed herein. Thesurfactants may be used as emulsifiers, wetting agents, dispersants,and/or agents to improve spreadability. Additionally, surfactants may beused as adjuvants and agents to control spin drift.

The present disclosure provides surfactants for agricultural products inthe form of siloxane derivatives of amino acids that have surface-activeproperties. The amino acids may be naturally occurring or syntheticamino acids, or they may be obtained via ring-opening reactions ofmolecules such as lactams, for instance caprolactam. The amino acids maybe functionalized with different types of siloxane groups to formcompounds with surface-active properties. Characteristically, thesecompounds may have low critical micelle concentrations (CMC) and/or theability to reduce the surface tension of a liquid.

The present disclosure provides a formulation for a pesticide or plantgrowth regulator, comprising at least one surfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; a pesticide or plant growth regulator;and a water-insoluble solvent.

The present disclosure further provides a formulation for a fungicide,comprising at least one surfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; an optional co-surfactant, and anoptional carrier agent, such as a solvent or solid carrier.

The present disclosure also provides a formulation for an herbicide,comprising at least one surfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; one or more herbicides, a water-insolublesolvent, and water.

The present disclosure further provides a formulation for aninsecticide, comprising at least one surfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; an insecticide, an optional antifoamingagent, an optional antifreezing agent, and water.

The above mentioned and other features of the disclosure, and the mannerof attaining them, will become more apparent and will be betterunderstood by reference to the following description of embodimentstaken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a plot of surface tension versus concentration forSurfactant 2, with a chloride counterion measured at pH=7 as describedin Example 1b.

FIG. 2 shows a plot of surface tension versus concentration forSurfactant 3 as described in Example 2b.

FIG. 3 shows a plot of dynamic surface tension as change in surfacetension versus time for Surfactant 3 as described in Example 2b.

FIG. 4 shows a plot of surface tension versus concentration forSurfactant 4 as described in Example 3b.

FIG. 5 shows a plot of dynamic surface tension as change in surfacetension versus time for Surfactant 4 as described in Example 3b.

FIG. 6 shows a plot of surface tension versus concentration forSurfactant 5 as described in Example 4b.

FIG. 7 shows a plot of dynamic surface tension as change in surfacetension versus time for Surfactant 5 as described in Example 4b.

DETAILED DESCRIPTION

As used herein, the phrase “within any range using these endpoints”literally means that any range may be selected from any two of thevalues listed prior to such phrase regardless of whether the values arein the lower part of the listing or in the higher part of the listing.For example, a pair of values may be selected from two lower values, twohigher values, or a lower value and a higher value.

As used herein, the word “alkyl” means any saturated carbon chain, whichmay be a straight or branched chain.

As used herein, the phrase “surface-active” means that the associatedcompound is able to lower the surface tension of the medium in which itis at least partially dissolved, and/or the interfacial tension withother phases, and, accordingly, may be at least partially adsorbed atthe liquid/vapor and/or other interfaces. The term “surfactant” may beapplied to such a compound.

With respect to the terminology of inexactitude, the terms “about” and“approximately” may be used, interchangeably, to refer to a measurementthat includes the stated measurement and that also includes anymeasurements that are reasonably close to the stated measurement.Measurements that are reasonably close to the stated measurement deviatefrom the stated measurement by a reasonably small amount as understoodand readily ascertained by individuals having ordinary skill in therelevant arts. Such deviations may be attributable to measurement erroror minor adjustments made to optimize performance, for example. In theevent it is determined that individuals having ordinary skill in therelevant arts would not readily ascertain values for such reasonablysmall differences, the terms “about” and “approximately” can beunderstood to mean plus or minus 10% of the stated value.

The present disclosure provides formulations of agricultural products,such as pesticides, plant growth regulators, fungicides, insecticides,and herbicides.

I. Pesticide and Plant Growth Requlator Formulations

Active agricultural agents such as pesticides have conventionally beenprovided to the end-user in different concentrated forms to be dilutedin water or other suitable medium to a dilute ready-to-use formulationby the end-user. Such concentrated forms include solid formulations,e.g. powders, and liquid formulations. In many applications, liquidformulations are preferred as problems of dusting of toxic powders andslow dissolution in the diluent may be avoided.

The liquid concentrated formulations include so-called emulsionconcentrates and soluble liquid concentrates. An emulsion concentratecomprises a pesticide, a water-insoluble solvent, and an emulsifier, andwhen added to the water, it spontaneously, or after mixing, forms anoil-in-water emulsion, the agricultural active primarily being presentin the emulsion droplets. This type of concentrated formulation isespecially suitable for agricultural actives that are waterinsoluble/have low water solubility, and where the recommendedconcentration in the ready-to-use formulation exceeds the solubility ofthe agricultural active.

The present disclosure provides a pesticide or plant growth regulatorformulation with a high concentration of the agriculturally activeagent, suitable for long term storage and delivery to the end user, whoeventually will treat plants by contacting the plant with anagricultural formulation prepared from the concentrated pesticidalformulation described herein.

The pesticide formulations of the present disclosure may include anagriculturally active agent (a pesticide or a plant growth regulator),one or more surfactants or co-surfactants chosen from one or moresurfactant classes, and a water-insoluble solvent.

1. Pesticide

The term “pesticide,” as used herein, is well known in the art and isdescribed at least by the Environmental Protection Agency (EPA), in theFederal Insecticide, Fungicide, and Rodenticide Act (FIFRA), in theInsecticides and Environmental Pesticide Control Subchapter (7 U.S.C. §136(u)), in the Code of Federal Regulations (CFR) relating to the“Protection of Environment,” and in the Regulations of the EPA in 40 CFR§ 152.3. A pesticide is typically recognized in the art as a substancethat is used for preventing, destroying, repelling, regulating, and/ormitigating any pest. A pest is an organism that is deleterious to man orthe environment but does not include any internal parasite of living manor other living animal or any fungus, bacterium, virus, or othermicroorganism on or in living man or other living animals. Saiddifferently, the terminology “pest” does not typically include anyorganism that infects or sickens humans or animals. In addition, theterminology “pesticide,” as used herein, does not typically include anyhuman or animal drugs or pharmaceuticals, any article that is a “newanimal drug” as defined in the art, any liquid sterilant applied to adevice used in the human body, and/or any products intended for useagainst fungi, bacteria, viruses, or other microorganisms in or onliving man or living animal. Moreover, the pesticide of this disclosuredoes not typically include drugs or pharmaceuticals used to controldiseases of humans or animals (such as livestock and pets).

As used herein, the term “plant growth regulator” refers to a compound,which through physiological action will accelerate or retard the rate ofgrowth or rate of maturation or otherwise alter the behavior ofornamental or crop plants or the products thereof.

Pesticides and plant growth regulators especially contemplated for usein the present invention are organic compounds, preferably syntheticorganic compounds. Suitable pesticides and plant growth regulatorsinclude triazoles, strobilurins, alkylenebis(dithiocarbamate) compounds,benzimidazoles, phenoxy carboxylic acids, benzoic acids, ureas,sulfonylureas, triazines, pyridine carboxylic acids, neonicotinides,amidines, organophosphates, and pyrethroids. The pesticide may have awater solubility of 1 g/L or less.

In a concentrated formulation of the present disclosure, the pesticideor plant growth regulator may be present in an amount of about 5 wt. %or greater, about 10 wt. % or greater, about 15 wt. % or greater, about20 wt. % or greater, or about 25 wt. % or lower, about 30 wt. % orlower, about 35 wt. % or lower, about 40 wt. % or lower, or within anyrange using these endpoints, by weight of the composition.

2. Surfactant

The pesticide formulations of the present disclosure comprise one ormore surfactants, also referred to as the surfactant system. Thesurfactant system is included to emulsify the composition, and/or to actas an adjuvant. The surfactant system comprises at least one surfactant,which may be an amphoteric surfactant, a zwitterionic surfactant, acationic surfactant, a nonionic surfactant, and optionally at least oneother surfactant, which may be an amphoteric surfactant, a zwitterionicsurfactant, a cationic surfactant, a nonionic surfactant, or acombination thereof. Such surfactants should be physically andchemically compatible with the essential components described herein, orshould not otherwise unduly impair product stability, aesthetics, orperformance.

Suitable surfactants for use in the pesticide formulations of thepresent disclosure include one or more surfactants and/or co-surfactantsof Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; and an optional counterion associated withthe compound which, if present, is selected from the group consisting ofchloride, bromide, and iodide.

In particular, suitable surfactants or co-surfactants may include one ormore of any of Surfactants 1-6 described herein.

The concentration of the surfactant system in the pesticide formulationmay range from about 20 wt. % or greater, about 30 wt. % or greater,about 40 wt. % or greater, or about 50 wt. % or lower, about 60 wt. % orlower, about 70 wt. % or lower, or about 80 wt. % or lower, or withinany range using these endpoints, by weight of the composition.

3. Water-Insoluble Solvent

The pesticide formulations of the present disclosure may include awater-insoluble solvent. A solvent is considered water-insoluble if itswater solubility is about 10 g/L of water or less, about 5 g/L of wateror less, about 1 g/L of water or less, or about 0.1 g/L or water or lessat 20° C.

Suitable water-insoluble solvents may include aromatic solvents such asthose sold under the tradename of Solvesso, and water-insolublealcohols, such as linear or branched, aliphatic or aromatic, saturatedor unsaturated alcohols with at least 6 carbon atoms.

4. Other Additives

The pesticide formulation may include other additives such as additionalsurfactants, water, thickeners, deposition enhancers, drift controlagents, salts, stabilizers, penetrants, spreading agents, wettingagents, building agents, extending agents, emulsifiers, dispersants,suspending agents, plant penetrants, translocators, oils, activators,foliar nutrients, compatibility agents, drift retardants, foamretardants, buffers, inverting agents, soil penetrants, stabilizingagents, UV filters, feeding stimulants, washing agents, sinking agents,binders, liquid carriers, dry carriers such as attapulgite, kaolinite,vermiculite, starch polymers, corn cob, and combinations thereof. Thepesticide formulation may also include additional chemical compoundsthat are not pesticides, such as activators, anti-feedants, anti-foulingagents, attractant agents, chemosterilants, disinfectant agents,fumigant agents, pheromones, repellent agents, defoliants, desiccants,insect growth regulators, plant growth regulators, synergists,adjuvants, and combinations thereof.

These additives may be independently present in the pesticidalformulation in an amount of about 0 wt. % greater, about 5 wt. % orgreater, about 10 wt. % or greater, about 15 wt. % or greater, or about20 wt. % or lower, about 25 wt. % or lower, about 30 wt. % or lower, orwithin any range using these endpoints.

Additional surfactants, such as additional anionic, non-ionic, cationic,amphoteric, and zwitterionic surfactants, may present in theconcentrated composition at a concentration of about 5 wt. % or greater,about 10 wt. % or greater, about 15 wt. % or greater, about 20 wt. % orgreater, or about 25 wt. % or lower, about 30 wt. % or lower, about 35wt. % or lower, about 40 wt. % or lower, or within any range using theseendpoints, by weight of the composition.

Water may be present in the concentrated composition at a concentrationof about 0 wt. % or greater, about 5 wt. % or greater, about 10 wt. % orgreater, about 20 wt. % or greater, about 30 wt. % or greater, or about35 wt. % or lower, about 45 wt. % or lower, about 55 wt. % or lower,about 65 wt. % or lower, or within any range using these endpoints, byweight of the composition.

Polymers may be included in the concentrated composition, as thickeners,deposition enhancers, or drift control agents. Suitable polymers mayinclude polysaccharide ethers and synthetic polymers.

Water-soluble organic solvents, such as glycol ethers, such as butyldiglycol, N-formyl-morpholine, shorter aliphatic alcohols, propylenecarbonate, etc. may be present in the pesticidal formulation at a weightratio water-soluble organic solvent:water-insoluble organic solvent ofat most 1:2.

5. Method of Making

The method includes the step of combining the surfactant system, thepesticide, and optionally the solvent. This step may also include addingany additives described above. The aforementioned components andcompounds may be added in any order to one or more of each other and inany amount and in one or more individual steps, e.g. in whole or inparts.

6. Method of Use

The concentrated pesticidal formulation of the present disclosure may bein liquid form at room temperature and atmospheric pressure, with theagriculturally active ingredient solubilized therein.

The concentrated pesticidal formulation is intended to be mixed with anaqueous medium, typically tap water, before end use. The concentratedcomposition is added to a tank, before, simultaneously with or after,addition of the aqueous medium (water) to the tank. The concentratedpesticidal composition is therewith diluted to a suitable concentrationof the agriculturally active.

The water content in the diluted pesticidal formulation of the presentdisclosure may be from about 75 wt. % or greater, about 90 wt. % orgreater, about 99 wt. % or greater, or about 99.9 wt. % or greater,based on the total weight of the diluted composition, and willultimately depend on the amount of water needed to dilute theagriculturally active ingredient in the concentrated pesticidalformulation of the present disclosure to the desired concentration inthe ready-to-use composition.

When mixed with and diluted in the aqueous medium, the agriculturallyactive is evenly distributed in the aqueous medium, in the form of asolution or a fine emulsion and can be diluted substantially without anycrystal growth occurring.

Plants may be treated with the diluted, ready-to-use pesticidalformulation by contacting the plant to be treated with the dilutedcomposition in any manner conventionally used. As used herein, the term“plant” refers not only to the stem, leave and fruit of the plant,visible above ground, but also to the roots as well as seeds. The amountof active ingredient contacted with the plant is preferably sufficientfor the active ingredient to exercise its pesticidal or plant growthregulating activity, i.e. an effective amount.

II. Fungicide Formulations

The present disclosure provides formulations of fungicides. Thefungicide formulation may be in solid or liquid form. Fungi againstwhich the formulation may be employed include: Basidiomycetes,Ascomycetes, Adalomycetes or Fungi imperfecti-type fungi, especiallyheifers, oidia, eyespot, fusarioses, Fusarium roseum, Fusarium nivale,net blotch, leaf blotch, Septoria spot and sin Rhizoctonia. Theseharmful fungi can cause diseases in most vegetables and plants, butespecially in cereals such as wheat, barley, rye, oats or their hybrids,and rice and corn.

The fungicide formulation may include a fungicide, an emulsifiercomponent, such as one or more surfactants or co-surfactants chosen fromone or more surfactant classes, an optional co-emulsifier, and anoptional carrier agent, such as a solvent or solid carrier.

1. Fungicide

The fungicidal formulation includes a fungicide. Suitable fungicidesinclude, but are not limited to: azoxystrobin, benalaxyl, carbendazim,chlorothalonil, cupfer, cymoxanil, cyproconazol, diphenoconazol,dinocap, epoxyconazol, fluazinam, flusilazol, flutriafol, folpel,fosetyl alumnium, kresoxim methyl, hexaconazol, mancozeb, metalaxyl,metconazol, myclobutanil, ofurace, phentinhydroxide, prochloraz,pyremethanil, soufre, tebucanazol and tetraconazol, and mixturesthereof. Suitable herbicides include, but are not limited to: alachlor,acloniphen, acetochlor, amidosulfuron, aminotriazol, atrazin, bentazon,biphenox, bromoxyl octanoate, bromoxynil, clethodim,chlodinafop-propargyl, chloridazon, chlorsulfuron, chlortoluron,clomazon, cycloxydim, desmedipham, dicamba, dicyclofop-methyl, diurea,difluphenicanil, dimithenamid, ethofumesat, fluazifop,fluazifop-p-butyl, fluorochloridon, fluroxypyr, glufosinat, glyphosate,galoxyfop-R, ioxynil octanoate, isoproturon, isoxaben, metamitron,metazachlor, metolachlor, metsulfuron-methyl, nicosulfuron, notflurazon,oryzalin, oxadiazon, oxyfluorphen, paraquat, pendimethalin,phenmedipham, phenoxyprop-p-ethyl, propaquizafop, prosulfocarb,quizalofop, sulcotrion, sulphosat, terbutylazin, triasulfuron,trichlorpyr, triflualin and triflusulforon-methyl which may be usedindividually or in admixture with one another.

The amount of fungicide may be about 1 wt. % or greater, about 5 wt. %or greater, about 10 wt. % or greater, about 20 wt. % or greater, about30 wt. % or greater, about 40 wt. % or greater, or about 50 wt. % orless, about 60 wt. % or less, or about 70 wt. % or less, about 80 wt. %or less, about 90 wt. % or less, or any range combination using theseendpoints, based on the total weight of the liquid fungicidalformulation.

2. Surfactant

The fungicide formulations of the present invention comprise one or moresurfactants, also referred to as the surfactant system. The surfactantsystem may be used as a dispersing or wetting agent. The surfactantsystem may also be used as an emulsifier component to form a stableemulsion of the liquid fungicide formation when prepared foragricultural applications. The emulsifier component may also be used toform a stable emulsifiable concentrate. The surfactant system comprisesat least one surfactant, which may be an amphoteric surfactant, azwitterionic surfactant, a cationic surfactant, a nonionic surfactant,and optionally at least one other surfactant, which may be an amphotericsurfactant, a zwitterionic surfactant, a cationic surfactant, a nonionicsurfactant, or a combination thereof.

Suitable surfactants for use in the fungicidal formulations of thepresent disclosure include one or more surfactants and/or co-surfactantsof Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; and an optional counterion associated withthe compound which, if present, is selected from the group consisting ofchloride, bromide, and iodide.

In particular, suitable surfactants or co-surfactants may include one ormore of any of Surfactants 1-6 described herein.

The total amount of the one or more surfactants in the fungicidalformulation may be about 1 wt. % or greater, about 5 wt. % or greater,about 10 wt. % or greater, or about 15 wt. % or less, about 20 wt. % orless, about 25 wt. % or less, about 30 wt. % or less, about 35 wt. % orless, or within any range using these endpoints.

3. Co-Emulsifier or Co-Surfactant

The fungicide composition may include an optional co-emulsifier orco-surfactant. The optional co-surfactant may be an anionic surfactantand/or a non-ionic surfactant, and may include those surfactants of thepresent disclosure, as well as others. For example, the anionicsurfactant include the surfactants of the present disclosure or anyknown in the art, and may include alkali, alkaline earth or ammoniumsalts of fatty acids, such as potassium stearate, alkyl sulfates, alkylether sulfates, alkylsulfonates or iso-alkylsulfonates,alkylnaphthalenesulfonates, alkyl methyl ester sulfonates, acylglutamates, alkylsulfosuccinates, sarcosinates such as sodium lauroylsarcosinate or taurates, and combinations thereof. The anionicsurfactant may be present in the emulsifier component in any amount.

The non-ionic emulsifier may include those surfactants of the presentdisclosure or any known in the art, such as alkoxylated animal orvegetable fats and oils such as corn oil ethoxylates, soybean oilethoxylates, castor oil ethoxylates, tallow fatty ethoxylates, glycerolesters such as glycerol monostearate, fatty alcohol alkoxylates andoxoalcohol alkoxylates, fatty acid alkoxylates such as oleic acidethoxylates, alkylphenol alkoxylates such as isononylphenol ethoxylates,fatty amine alkoxylates, fatty acid amide alkoxylates, sugar surfactantssuch as sorbitan fatty acid esters (e.g. sorbitan monooleate, andsorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkylpolyglycosides, N-alkylgluconamides, alkylmethyl sulfoxides,alkyldimethylphosphine oxides such as tetradecyldimethylphosphine oxide,and combinations thereof.

4. Carrier Agent

The fungicidal formulation of the present disclosure may include acarrier agent. As used herein, the term “carrier” refers to a materialof natural or synthetic, organic or inorganic form which, when combinedwith the active ingredient, promotes its application to the plant, seedsor soil. Therefore, this carrier is usually inert, but must also beagriculturally acceptable, especially for the plant to be treated. Thecarrier may be solid (clay, natural or synthetic silicates, silicondioxide, resins, waxes or solid fertilizers, etc.) or liquid (water,alcohols, ketones, petroleum fractions, aromatic or paraffinichydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.).

5. Other Additives

The fungicide formulation may include other additives such asstabilizers, penetrants, spreading agents, wetting agents, buildingagents, extending agents, emulsifiers, dispersants, suspending agents,plant penetrants, translocators, oils, activators, foliar nutrients,compatibility agents, drift retardants, foam retardants, buffers,inverting agents, soil penetrants, stabilizing agents, UV filters,feeding stimulants, washing agents, sinking agents, binders, liquidcarriers, dry carriers such as attapulgite, kaolinite, vermiculite,starch polymers, corn cob, and combinations thereof. The pesticideformulation may also include additional chemical compounds that are notpesticides, such as activators, anti-feedants, anti-fouling agents,attractant agents, chemosterilants, disinfectant agents, fumigantagents, pheromones, repellent agents, defoliants, desiccants, insectgrowth regulators, plant growth regulators, synergists, adjuvants, andcombinations thereof.

These additives may be independently present in the pesticidalformulation in an amount of about 0 wt. % greater, about 5 wt. % orgreater, about 10 wt. % or greater, about 15 wt. % or greater, or about20 wt. % or lower, about 25 wt. % or lower, about 30 wt. % or lower, orwithin any range using these endpoints.

6. Fungicidal Emulsion

The liquid fungicidal formulation may be added to water or anothersolvent to form an agricultural emulsion at point of sale and/or use.Typically, well-formed agricultural emulsions are milky in color,spontaneously bloom (i.e., form), and have sufficient stability forefficacious application. However, the fungicidal emulsions of thepresent disclosure are not limited to such parameters and may have othercharacteristics that are indicative of successful emulsion formation.

The present disclosure provides an aqueous fungicidal formulation thatincludes the aforementioned fungicidal formulation and water. The liquidfungicide formulation may be combined with the water in a spray tank orin an independent tank prior to addition to a spray tank. For example,the liquid fungicide formulation may be added to an independentcontainer and/or a spray tank with the water or separate from the water.The terminology “diluted” describes that the agricultural liquidfungicidal formulation including the water.

The water of the diluted fungicidal formulation may be present in anamount of about 5 wt. % or greater, about 10 wt. % or greater, about 20wt. % or greater, about 30 wt. % or greater, about 40 wt. % or greater,about 50 wt. % or greater, or about 60 wt. % or lower, about 70 wt. % orlower, about 80 wt. % or lower, about 90 wt. % or lower, about 99 wt. %or lower, about 99.5 wt. % or lower, or within any range using theseendpoints, of the diluted fungicidal formulation.

The fungicide may be present in the diluted fungicidal formulation inamounts from about 0.00001 wt. % or greater, about 0.0001 wt. % orgreater, about 0.001 wt. % or greater, about 0.01 wt. % or greater,about 0.1 wt. % or greater, about 1 wt. % or greater, or about 2 wt. %or lower, about 4 wt. % or lower, about 6 wt. % or lower, about 8 wt. %or lower, about 10 wt. % or lower, or within any range using theseendpoints.

The fungicide may be present in an amount (or in an amount equivalentto) of about 100 g/hectare or greater, about 200 g/hectare or greater,about 300 g/hectare or greater, about 400 g/hectare or greater, about500 g/hectare or greater, or about 600 g/hectare or lower, about 700g/hectare or lower, about 800 g/hectare or lower, about 900 g/hectare orlower, about 1000 g/hectare or lower, or within any range using theseendpoints.

7. Emulsifiable Concentrate

The present disclosure provides a fungicidal emulsion that may be formedusing an emulsifiable concentrate (also known in the art as an “EC”).The liquid fungicidal composition described above may be furtherdescribed as an EC or may not be an EC. The emulsifiable concentrate maybe a liquid that has a viscosity of about 1 cps or greater, 20 cps orgreater, 40 cps or greater, 60 cps or greater, 80 cps or greater, 100cps or greater, or 120 cps or lower, 140 cps or lower, 160 cps or lower,180 cps or lower, 200 cps or lower, or within any range using theseendpoints, at 25° C. to 200, 50 to 200, 100 to 200, or less than orequal to about 200, cps at 25° C. Without intending to be bound by anyparticular theory, it is believed that a viscosity of less than or equalto about 200 cps at 25° C. promotes blooming and efficient formation ofan emulsion when the emulsifiable concentrate is used.

The emulsifiable concentrate itself may be anhydrous, i.e., free ofwater. Alternatively, the emulsifiable concentrate may include water.The emulsifiable concentrate may include water in an amount of 5 wt. %or less, 2.5 wt. % or less, 1 wt. % or less, 0.5 wt. % or less, or 0.1wt. % or less. The emulsifiable concentrate may include less than 15,14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1, part by weight ofwater per 100 parts by weight of the emulsifiable concentrate. Theemulsifiable concentrate is a single oil-like, e.g. hydrophobic, phasethat does not include water. When added to water or another solvent, theemulsifiable concentrate may form a milky white agricultural emulsionthat blooms and that has little to no phase separation, as is describedin greater detail below.

The emulsifiable concentrate may include a single phase. In other words,the emulsifiable concentrate may not include a distinct non-polar phaseand a distinct polar phase but instead a single phase that includes theactive component (the fungicide), the surfactant system, the optionalco-surfactant, and/or the optional water-insoluble solvent. It is to beappreciated that the single phase may include partial phase separationbut does not typically include total phase separation. At lowtemperatures, phase separation may occur. The emulsifiable concentratemay be described as including or being the aforementioned surfactantsystem and the fungicide (e.g. without the optional solvent and/orwithout the optional co-surfactant.

8. Solid Formulation

For solid form compositions, reference may be made to powders ordispersions suitable for dusting, in particular particulate compositionswhich are extruded, extruded, or extruded. The solid formulations may beformed through impregnation of a carrier powder with the active agent,or by granulation of a powder.

The amount of active agent in these granular compositions may be about 1wt. % or greater, 10 wt. % or greater, 20 wt. % or greater, 30 wt. % orgreater, of about 40 wt. % or lower, about 50 wt. % or lower, about 60wt. % or lower, about 70 wt. % or lower, about 80 wt. % or lower, orwithin any range using these endpoints.

Wettable powder formulations (or spray powders) may include the activeagent in an amount of about 20 wt. % or greater, about 30 wt. % orgreater, about 40 wt. % or greater, or about 50 wt. % or greater, about60 wt. % or lower, about 70 wt. % or lower, about 80 wt. % or lower,about 90 wt. % or lower, about 95 wt. % or lower, or within any rangeusing these endpoints.

Wettable powder formulations may include wetting agents, such as asurfactant, which may include those surfactants of the presentdisclosure, in an amount of about 0 wt. % or greater, about 1 wt. % orgreater, about 2 wt. % or greater, or about 3 wt. % or lower, about 4wt. % or lower, about 5 wt. % or lower, or within any range using theseendpoints.

Wettable powder formulations may include a dispersant, such as asurfactant, which may include those surfactants of the presentdisclosure, in an amount of about 3 wt. % or greater, about 4 wt. % orgreater, about 5 wt. % or greater, about 6 wt. % or greater, or about 7wt. % or lower, about 8 wt. % or lower, about 9 wt. % or lower, or about10 wt. % or lower, or within any range using these endpoints.

Wettable powder formulations may include a solid carrier, which mayinclude any solid carrier known in the art, in an amount or about 0 wt.% or greater, about 1 wt. % or greater, about 2 wt. % or greater, about3 wt. % or greater, about 4 wt. % or greater, about 5 wt. % or greater,or about 6 wt. % or lower, about 7 wt. % or lower, about 8 wt. % orlower, about 9 wt. % or lower, about 10 wt. % or lower, or within anyrange using these endpoints.

Wettable powder formulations may contain one or more stabilizers and/orother additives, such as pigments, colorants, permeation agents,adhesion promoters or anti-caking agents.

In order to produce these wettable powder formulations or sprayablepowders, the active agent(s) are intimately mixed with the othercomponents in a suitable mixing apparatus, and the resulting mixture ismilled with mills or other suitable grinding equipment. Thus, sprayablepowders are obtained which have a wettability and suspendability. Thus,they can be suspended in arbitrary concentrations in water, and thesesuspensions are particularly useful for treating seeds in particular.

In addition to wettable powder formulations, pastes may also beproduced. The conditions and methods of preparation and use of thepastes are similar to those for wettable powders or spray powders.

Dispersible granular compositions may be prepared by agglomeration in asuitable granulation system to provide powder compositions similar towettable powder formulations.

III. Herbicide Formulation

The present disclosure further provides formulations of herbicides.These formulations may be applied to a plant in a herbicidally effectiveamount, and can effectively control one or more plant species of one ormore of the following genera without restriction: Abutilon, Amaranthus,Artemisia, Asclepias, Avena, Axonopus, Borreria, Brachiaria, Brassica,Bromus, Chenopodium, Cirsium, Commelina, Convolvulus, Cynodon, Cyperus,Digitana, Echinochloa, Eleusine, Elymus, Equisetum, Erodium, Helianthus,Imperata, Ipomoea, Kochia, Lolium, Malva, Oryza, Ottochloa, Panicum,Paspalum, Phalaris, Phragmites, Polygonum, Portulaca, Pteridium,Pueraria, Rubus, Salsola, Setaria, Sida, Sinapis, Sorghum, Triticum,Typha, Ulex, Xanthium and Zea.

The herbicidal formulations of the present disclosure may include anherbicide, and optional second herbicide, one or more surfactants chosenfrom one or more surfactant classes, a water-insoluble solvent, andwater.

1. Herbicide

The herbicide formulation of the present disclosure may includeherbicides or their water-soluble salts. Suitable herbicides may include2,4-D (2,4-dichlorophenoxyacetic acid), 2,4-DB(4-(2,4-dichlorophenoxy)butyric acid), aminocyclopyrachlor,aminopyralid, clopyralid, dicamba, glyphosate, MCPA, MCPB, picloram,triclopyr, or mixtures thereof.

The water-soluble salts of the herbicides herbicides may include saltscontaining one or more cations selected from the class of organoammonium cations, wherein the organo ammonium cations may have from 1 toabout 12 carbon atoms, such as organo ammonium cations include, forexample, isopropyl ammonium, diglycol ammonium (2-(2-aminoethoxy)ethanolammonium), dimethyl ammonium, diethyl ammonium, triethyl ammonium,monoethanol ammonium, dimethylethanol ammonium, diethanol ammonium,triethanol ammonium, triisopropanol ammonium, tetramethyl ammonium,tetraethylammonium, N,N,N-trimethylethanol ammonium (choline), andN,N-bis-(3-aminopropyl)methyl ammonium (BAPMA).

Additionally, the water-soluble salts of the herbicides may includesalts containing one or more cations selected from inorganic cationssuch as, for example, sodium and/or potassium.

In the case of acidic herbicides, such as auxin herbicides, theherbicide may be present in the herbicide formulation in an amount ofabout 100 grams acid equivalent per liter (g ae/L) or greater, about 200g ae/L or greater, about 300 g ae/L or greater, or about 400 g ae/L orlower, about 500 g ae/L or lower, about 600 g ae/L or lower, about 625 gae/L or lower, or within any range using these endpoints.

Some herbicide active agents described herein do not contain anacid-type functional group and, for these active ingredients, the terms“acid equivalent” and “acid equivalent basis” are not accurate todescribe the amount of the second herbicide present. Generally, in suchinstances, the terms “active ingredient” or “active ingredient basis”can be used to describe the amount of the second herbicide activeingredient present. For example, grams active ingredient per liter (gai/L) may be used in place of grams acid equivalent per liter (g ae/L),or grams active ingredient per kilogram (g ai/kg) may be used in placeof grams acid equivalent per kilogram (g ae/kg) when the activeingredient does not have an acid equivalent.

2. Optional Second Herbicide

Suitable second herbicides may be selected from, but are not limited to,esters of 4-CPA, 4-CPB, 4-CPP, 2,4-D, 3,4-DA, 2,4-DB, 3,4-DB, 2,4-DEB,2,4-DEP, 3,4-DP, 2,4,5-T, 2,4,5-TB, and 2,3,6-TBA, allidochlor,acetochlor, acifluorfen, aclonifen, alachlor, alloxydim, alorac,ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron,aminocyclopyrachlor esters, aminopyralid esters, amiprofos-methyl,amitrole, anilofos, anisuron, asulam, atraton, atrazine, azafenidin,azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin,bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide,bentazone, benzadox, benzfendizone, benzipram, benzobicyclon,benzofenap, benzofluor, benzoylprop, benzthiazuron, bicylopyrone,bifenox, bilanafos, bispyribac, bromacil, bromobonil, bromobutide,bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil,butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim,buturon, butylate, cafenstrole, cafenstrole, cambendichlor, carbasulam,carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA,CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine,chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop,chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlomitrofen,chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham,chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin,cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop,clomazone, clomeprop, clomeprop, cloprop, cloproxydim, clopyralidesters, cloransulam, CPMF, CPPC, credazine, cumyluron, cyanatryn,cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop,cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet,delachlor, desmedipham, desmetryn, di-allate, dicamba esters,dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P,diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron,difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate,dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano,dimidazon, dinitramine, dinitramine, dinofenate, dinoprop, dinosam,dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr,diuron, DMPA, DNOC, EBEP, eglinazine, endothal, epronaz, epronaz, EPTC,erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron,ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen,etnipromid, etnipromid, etnipromid, etobenzanid, EXD, fenasulam,fenasulam, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone,fenteracol, fenthiaprop, fentrazamide, fenuron, flamprop, flamprop-M,flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate,flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican,flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn,fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen,fluothiuron, flupoxam, flupoxam, flupropacil, flupropanate,flupyrsulfuron, fluridone, fluorochloridone, non-liquid fluoroxypyresters, fluoroxypyr-meptyl, flurtamone, fluthiacet, fomesafen,fomesafen, foramsulfuron, fosamine, furyloxyfen, glyphosate, halauxfen,halauxfen-methyl, halosafen, halosafen, halosulfuron, haloxydine,haloxyfop, haloxyfop-P, hexazinone, imazamethabenz, imazamox, imazapic,imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam,iodobonil, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam,isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin,isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole,isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron,MCPA esters, MCPA-thioethyl, MCPA-EHE, MCPB esters, mecoprop,mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine,mesosulfuron, mesotrione, metam, metamifop, metamifop, metamitron,metazachlor, metazosulfuron, metflurazon, methabenzthiazuron,methalpropalin, methazole, methiobencarb, methiozolin, methiuron,methiuron, methometon, methoprotryne, methyldymron, metobenzuron,metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron,metribuzin, metsulfuron, molinate, monalide, monisouron, monolinuron,monuron, morfamquat, naproanilide, napropamide, naptalam, neburon,nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,norflurazon, noruron, OCH, orbencarb, orthosulfamuron, oryzalin,oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron,oxaziclomefone, oxyfluorfen, parafluoron, paraquat, pebulate, pelargonicacid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone,pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl,phenobenzuron, picloram esters, picolinafen, pinoxaden, piperophos,pretilachlor, primisulfuron, procyazine, prodiamine, prodiamine,profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn,propachlor, propanil, propaquizafop, propazine, propham, propisochlor,propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin,prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil,pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen,pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid,pyriminobac, pyrimisulfan, pyrithiobac, pyrosulfotole, pyroxasulfone,pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop,quizalofop-P rhodethanil, rimsulfuron, saflufenacil, sebuthylazine,secbumeton, sethoxydim, siduron, simazine, simeton, simetryn,sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron,sulglycapin, swep, tebutam, tebuthiuron, tefuryltrione, tembotrione,tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton,terbuthylazine, terbutryn, tetrafluoron, thenylchlor, thiazafluoron,thiazopyr, non-liquid triclopyr esters, thidiazimin, thidiazuron,thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb,tiocarbazil, tioclorim, topramezone, tralkoxydim, tri-allate,triasulfuron, triaziflam, tribenuron, tricamba, tridiphane, trietazine,trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime,trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron,vemolate, xylachlor and mixtures and derivatives thereof.

The second herbicide is present, if used, in an amount of about 0 g ae/Lor greater, 0.1 g ae/L or greater, 10 g ae/L or greater, 50 g ae/L orgreater, 100 g ae/L or greater, or 200 g ae/L or lower, about 300 g ae/Lor lower, about 400 g ae/L or lower, or within any range using theseendpoints.

Some second herbicide active agents described herein do not contain anacid-type functional group and, for these active ingredients, the terms“acid equivalent” and “acid equivalent basis” are not accurate todescribe the amount of the second herbicide present. Generally, in suchinstances, the terms “active ingredient” or “active ingredient basis”can be used to describe the amount of the second herbicide activeingredient present. For example, grams active ingredient per liter (gai/L) may be used in place of grams acid equivalent per liter (g ae/L),or grams active ingredient per kilogram (g ai/kg) may be used in placeof grams acid equivalent per kilogram (g ae/kg) when the activeingredient does not have an acid equivalent

3. Surfactant

Suitable surfactants for use in the herbicide formulations of thepresent disclosure include one or more surfactants and/or co-surfactantsof Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; and an optional counterion associated withthe compound which, if present, is selected from the group consisting ofchloride, bromide, and iodide.

In particular, suitable surfactants or co-surfactants may include one ormore of any of Surfactants 1-6 described herein.

The herbicidal formulations may include one or more surfactants in anamount of about 0 wt. % or greater, about 2 wt. % or greater, about 4wt. % or greater, about 6 wt. % or greater, about 8 wt. % or greater, orabout 10 wt. % or lower, about 12 wt. % or lower, about 14 wt. % orlower, about 16 wt. % or lower, or within any range using theseendpoints.

4. Water-Insoluble Solvents

Suitable water-insoluble immiscible organic solvents include thosederived from or made from natural, non-petroleum sources such as, forexample, plants and animals, and include, vegetable oils, seed oils,animal oils and the like, such N,N-dimethylcaprylamide(N,N-dimethyloctanamide), N,N-dimethylcapramide(N,N-dimethyldecanamide), and mixtures thereof, which are availablecommercially as Agnique® AMD 810 and Agnique® AMD 10, from BASF Corp.(Florham Park, N.J.), Genegen®4166, Genegen® 4231 and Genegen®4296, fromClariant (Charlotte, N.C.), Hallcomid M-8-10 and Hallcomid M-10, fromStepan (Northfield, Ill.), and Amid DM10 and DM810 from AkzoNobel(Chicago, Ill.). Additional examples of naturally derived organicsolvents include the morpholine amides of caprylic/capric fatty acids(C₈/C₁₀) which are commercially available as JEFFSOL® AG-I730 Solventfrom Huntsman International LLC (The Woodlands, Tex.).

Other suitable water-insoluble solvents may include aromatichydrocarbons, mixed naphthalene and alkyl naphthalene fractions,aromatic solvents, particularly alkyl substituted benzenes such asxylene or propylbenzene fractions, and the like; C₁-C₆ esters of fattyacids derived from vegetable, seed or animal oils such as, methylcaproate, methyl caprylate, methyl caprate, methyl laurate, methylmyristate, methyl palmitate, methyl stearate, methyl oleate, methyllinoleate, methyl linolenate, and the like; ketones such as isophoroneand trimethylcyclohexanone (dihydroisophorone); acetate esters such as,methyl, ethyl, propyl, butyl, pentyl, hexyl, or heptyl acetate, and thelike; and cyclic alkyl carbonates such as propylene carbonate andbutylene carbonate, which are available as the JEFFSOL® alkylenecarbonates from Huntsman (The Woodlands, Tex.), and dibutyl carbonate,also from Huntsman, and mixtures of any of the water immiscible organicsolvents described herein.

The water-insoluble solvent may be present in the herbicidal formulationin an amount of about 0 wt. % or greater, about 10 wt. % or greater,about 20 wt. % or greater, or about 30 wt. % or lower, about 40 wt. % orlower, about 50 wt. % or lower, or within any range using theseendpoints.

5. Water

Water may be present in the herbicidal formulations of the presentdisclosure to serve as both an aqueous solvent and a carrier for theingredients in the described compositions.

The herbidical formulation of the present disclosure may include waterin an amount of about 200 g/L or greater, about 300 g/L or greater,about 400 g/L or greater, or about 500 g/L or lower, about 600 g/L orlower, about 700 g/L or lower, about 800 g/L or lower, or within anyrange using these endpoints.

6. Other Additives

The herbicidal formulation may include one or more additional compatibleingredients. These additional ingredients may include, for example, oneor more pesticides or other ingredients, which may be dissolved ordispersed in the composition and may be selected from acaricides,algicides, antifeedants, avicides, bactericides, bird repellents,chemosterilants, defoliants, desiccants, disinfectants, fungicides,herbicide safeners, herbicides, insect attractants, insecticides, insectrepellents, mammal repellents, mating disrupters, molluscicides,nematicides, plant activators, plant growth regulators, rodenticides,semiochemicals, synergists, and virucides. Also, any other additionalingredients providing functional utility such as, for example, antifoamagents, antimicrobial agents, buffers, corrosion inhibitors, dispersingagents, dyes, fragrants, freezing point depressants, neutralizingagents, odorants, penetration aids, sequestering agents, spray driftcontrol agents, spreading agents, stabilizers, sticking agents,viscosity-modifying additives, water soluble solvents and the like, maybe included in these compositions.

When the described herbicidal formulations are used in combination withthe additional active ingredients such as, for example, herbicide activeingredients, the compositions described herein can be formulated withthe other active ingredient or active ingredients as premixconcentrates, tank-mixed in water with the other active ingredient oractive ingredients for spray application or applied sequentially withthe other active ingredient or active ingredients in separate sprayapplications.

7. Method of Making

The herbicide formulations of the present disclosure may be prepared bythe steps of: 1) preparing a solution of the one or more secondherbicide in the organic solvent and a surfactant; 2) adding thesolution prepared in step 1) to a concentrated solution of awater-soluble salt of an herbicide in water with good mixing to form aclear solution; and 3) optionally, adding any additional compatibleactive or inert ingredients.

Alternatively, the herbicide formulations of the present disclosure maybe prepared by the steps of: 1) providing a second herbicide that is aliquid and, optionally, mixing it with the organic solvent and asurfactant; 2) adding the composition prepared in step 1) to aconcentrated solution of a water-soluble salt of an herbicide in waterwith good mixing to form a clear solution; and 3) optionally, adding anyadditional compatible active or inert ingredients.

Suitable water compatible ingredients that may be added to the herbicideformulations include, but are not limited to, water soluble or waterinsoluble dispersing surfactants, such as the surfactants of the presentdisclosure, water insoluble active ingredients and optionally, otherinert ingredients such as pH buffers, wetting agents, antifreeze agents,antifoam agents, and biocides.

8. Method of Use

The aqueous herbicidal formulations described herein may optionally bediluted in an aqueous spray mixture for agricultural application such asfor weed control in crop fields or in turf. Such herbicidal formulationsare typically diluted with an inert carrier, such as water, beforeapplication. The diluted herbicidal formulations, which are usuallyapplied, for example, to weeds, the locus of weeds, or the locus ofwhere weeds may eventually emerge, may contain the agriculturally activeagent (the herbicide) in an amount of about 0.0001 wt. % or greater,about 0.001 wt. % or greater, about 0.01 wt. % or greater, about 0.1 wt.% or greater, about 1 wt. % or greater, or about 2 wt. % or lower, about3 wt. % or lower, about 4 wt. % or lower, or about 5 wt. % or lower, orwithin any range using these endpoints. The herbicide formulations ofthe present disclosure can be applied, for example, to weeds or theirlocus by the use of conventional ground or aerial sprayers, by additionto irrigation water and by other conventional means known to thoseskilled in the art.

The herbicide formulations of the present disclosure may be used incontrolling undesirable vegetation in crops possessing single, multipleor stacked genomic traits conferring tolerance to one or more herbicidechemistries and/or inhibitors with single or multiple modes of action.

IV. Insecticide Formulations

The present disclosure also provides formulations of insecticides. Suchformulations may be in liquid or solid forms, such as emulsifiableconcentrates, oil in water (0/W) emulsions, suspension concentrates, andwettable powders.

The insecticide formulation may include an insecticide, one or moresurfactants chosen from one or more surfactant classes, an optionalantifoaming agent, an optional antifreezing agent, and water.

1. Insecticide

Suitable insecticides may include one or more of pyrethroids, such as asynthetic pyrethroid; an organophosphate compound, such aschlorpyrifos-ethyl, chlorpyrifos-methyl, pirimiphos-methyl,fenitrothion; a phenyl ether such as pyriproxyfen; a benzoylurea, suchas flufenoxuron; a carbamate, such as fenoxycarb, carbosulfan;nicotinoids, such as acetamiprid; pyridinecarboxamides, such asflonicamid; and/or others. The pyrethroid may be selected from one ormore of bifenthrin, zeta-cypermethrin, alpha-cypermethrin,tetra-methrin, lambda-cyhalothrin, fenvalerate, cyfluthrin,bio-resmethrin, permethrin, delta-methrin.

The insecticide may be present in the insecticide formulation in anamount, measured in weight per volume, of about 1% or greater, about 5%or greater, about 10% or greater, or about 15% or less, about 20% orless, or within any range using these endpoints.

2. Surfactants

The insecticide formulation may include one or more surfactants chosenfrom one or more surfactant classes, collectively referred to as thesurfactant system.

Suitable surfactants for use in the insecticide formulations of thepresent disclosure include one or more surfactants and/or co-surfactantsof Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; and an optional counterion associated withthe compound which, if present, is selected from the group consisting ofchloride, bromide, and iodide.

In particular, suitable surfactants or co-surfactants may include one ormore of any of Surfactants 1-6 described herein.

The surfactant system may be present in the insecticide formulation inan amount, measured in weight per volume, of about 1% or greater, about5% or greater, about 10% or greater, about 15% or greater, or about 20%or less, about 25% or less, about 30% or less, about 35% or less, about40% or less, or within any range using these endpoints.

3. Optional Antifoaming Agent

The optional antifoaming agent in the insecticide formulation mayinclude silicone emulsions, and/or surfactants, such as the surfactantsof the present disclosure.

The antifoaming agent may be present in the insecticide formulation inan amount, measured in weight per volume, of about 0.0% or greater,about 0.1% or greater, about 0.2% or greater, about 0.3% or greater,about 0.4% or greater, about 0.5% or greater, or about 0.6% or lower,about 0.7% or lower, about 0.8% or lower, about 0.9% or lower, about1.0% or lower, or within any range using these endpoints.

4. Optional Antifreezing Agent

The insecticide formulation may include an optional antifreezing agent.Suitable antifreezing agents may include diols, such as alkyldiols ordialkyldiols.

The insecticide formulation may include an antifreezing agent in anamount, measured in weight per volume, of about 0% or greater, about 1%or greater, about 2% or greater, about 3% or greater, about 4% orgreater, about 5% or greater, or about 6% or lower, about 7% or lower,about 8% or lower, about 9% or lower, about 10% or lower, or within anyrange using these endpoints.

5. Water

The insecticide formulation may include water in an amount, measured inweight per volume, of about 25% or greater, about 30% or greater, about35% or greater, about 40% or greater, about 45% or greater, about 50% orgreater, about 55% or greater, or about 60% or lower, about 65% orlower, about 70% or lower, about 75% or lower, about 80% or lower, about85% or lower, about 90% or lower, about 95% or lower, about 98% orlower, or within any range using these endpoints.

6. Other Additives

The insecticide formulations of the present disclosure may includeviscosity modifiers. Such viscosity modifiers may include thickeningagents, such as cellulose derivatives, polyacrylamides, polyvinylalcohols, polyvinyl pyrollidones, and natural gums.

Viscosity modifiers may be present in the insecticidal formulation inany amount suitable to modify the viscosity to the desired level.

The insecticide formulations of the present disclosure may also includepreservatives. Suitable preservatives include methylparaben.

Preservatives may be present in the insecticide formulation in anamount, measured as weight per volume, of 0.0% or greater, 0.1% orgreater, or 0.2% or less, or within any range using these endpoints.

V. Adjuvants

In addition to the uses described above, the surfactants of the presentdisclosure may be used as adjuvants in formulations agriculturallyactive agents, such as pesticides, plant growth regulators, herbicides,fungicides, and insecticides. Adjuvant compounds may be employed toimprove one or more properties of formulations of agriculturally activeagents, such as for example, storage stability, ease of handling,pesticide efficacy against a target organism.

VI. Spray Drift Reducing Agents

Spray drift refers to the unintentional diffusion of pesticides andother agriculturally active agents, including off-target contamination.This can lead to damage in human health, environmental contamination,and property damage. The surfactants of the present disclosure may beused to reduce the amount of driftable fines of formulations ofagriculturally active agents in both aerial and ground sprayapplications.

The surfactants of the present disclosure, and mixtures thereof, can beincorporated into an aqueous spray mixture, for example, by beingtank-mixed directly with a diluted formulation of an agriculturallyactive agent, such as a pesticide, plant growth regulator, fungicide,herbicide, or insecticide.

The optimum spray droplet size depends on the application for which thecomposition is used. If droplets are too large, there will be lesscoverage by the spray, e.g., large droplets will land in certain areaswhile areas in between will receive little or no spray coverage. Themaximum acceptable droplet size may depend on the amount of compositionbeing applied per unit area and the need for uniformity in spraycoverage. Smaller droplets provide more even coverage, but are moreprone to drift during spraying. Thus, application parameters such asuniformity in spray coverage must be balanced against the tendency forsmaller droplets to drift. For example, if it is particularly windyduring spraying, larger droplets may be needed to reduce drift, whereason a calmer day, smaller droplets may be acceptable. In addition to thephysical properties of a particular aqueous composition, spray dropletsize may also depend on the spray apparatus, e.g., nozzle size andconfiguration.

The reduction in spray drift may result from a variety of factorsincluding a reduction in the production of fine spray droplets (<150 μmminimum diameter) and an increase in the volume median diameter (VMD) ofthe spray droplets. In any event, for a given spray apparatus,application, and conditions, and based on the surfactant used, themedian diameter of the plurality of spray droplets created using thesurfactants described herein is increased above that of a spraycomposition that does not include the surfactants of the presentdisclosure.

VII. Surfactants

The present disclosure provides surfactants for use in agriculturalproducts in the form of siloxane derivatives of amino acids. The aminoacids may be naturally occurring or synthetic, or they may be obtainedfrom ring-opening reactions of lactams, such as caprolactam. Thecompounds of the present disclosure have been shown to havesurface-active properties, and may be used as surfactants and wettingagents, for example. In particular, the present disclosure providescompounds of Formula I, shown below:

wherein R¹ and R² may be the same or different, and are at least onegroup selected from the group consisting of C₁-C₆ alkyl, optionally theC₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfur atomsor substituents that include one or more of these atoms, the alkyl chainmay be optionally substituted with one or more substituents selectedfrom the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate;

n is an integer from 1 to 12;

the terminal nitrogen is optionally further substituted with R³, whereinR³ is selected from the group consisting of hydrogen, oxygen, hydroxyl,and C₁-C₆ alkyl; and

an optional counterion may be associated with the compound and, ifpresent, the counterion may be selected from the group consisting ofchloride, bromide, and iodide.

The present disclosure further provides for compounds of Formula Ia:

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate;

m is an integer from 1 to 6;

the terminal nitrogen is optionally further substituted with R³, whereinR³ is selected from the group consisting of hydrogen, oxygen, and C₁-C₆alkyl wherein the alkyl chain is optionally substituted with one or moresubstituents selected from the group consisting of carboxyl,carboxylate, and sulfonate; and

an optional counterion may be associated with the compound and, ifpresent, the counterion may be selected from the group consisting ofchloride, bromide, and iodide.

The present disclosure additionally provides for compounds of FormulaIb:

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate;

p is 5;

the terminal nitrogen is optionally further substituted with R³, whereinR³ is selected from the group consisting of hydrogen, oxygen, and C₁-C₆alkyl, wherein the alkyl chain is optionally substituted with one ormore substituents selected from the group consisting of carboxyl,carboxylate, and sulfonate; and

an optional counterion may be associated with the compound and, ifpresent, the counterion may be selected from the group consisting ofchloride, bromide, and iodide.

One specific compound provided by the present disclosure is6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide(Surfactant 1), having the following formula:

A second specific compound provided by the present disclosure is6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexaminiumchloride (Surfactant 2), having the following formula:

A third specific compound provided by the present disclosure is 36-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide (Surfactant 3), having thefollowing formula:

A fourth specific compound provided by the present disclosure is6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-amineoxide (Surfactant 4), having the following formula:

In the structure above, the notation “N-+0” is intended to convey anon-ionic bonding interaction between nitrogen and oxygen.

A fifth specific compound provided by the present disclosure is4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate(Surfactant 5), having the following formula:

A sixth specific compound provided by the present disclosure is5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate(Surfactant 6), having the following formula

These compounds may be synthesized by various methods. One such methodincludes reacting an amino acid, such as an N-alkylated or N-acylatedamino acid, with a siloxane to convert the amino acid C-terminus to thedesired siloxane derivative. The amino acid N-terminus may be furtherprotonated, alkylated, or oxidized to yield a quaternary amine or anN-oxide, for example.

The amino acid may be naturally occurring or synthetic or may be derivedfrom a ring opening reaction of a lactam, such as caprolactam. Thering-opening reaction may be either an acid or alkali catalyzedreaction, and an example of an acid catalyzed reaction is shown below inScheme 1.

The amino acid may have as few as 1 or as many as 12 carbons between theN- and C-terminii. The alkyl chain may be branched or straight. Thealkyl chain may be interrupted with nitrogen, oxygen, or sulfur. Thealkyl chain may be further substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carboxyl, and carboxylate. The N-terminal nitrogen may beacylated or alkylated with one or more alkyl groups. For example, theamino acid may be 6-(dimethylamino)hexanoic acid.

The siloxane may be substituted with one or more alkoxy groups, such asmethoxy, ethoxy, isopropoxy, tertiary butoxy, and others. The siloxanemay be further substituted with one or more alkyl groups, such aspropyl, wherein the alkyl group may yet be further substituted with anappropriate functional group to permit coupling of the siloxane to theamino acid, such as a nitrogen. For example, the siloxane may be3-aminopropyltris(trimethylsiloxy)silane.

The siloxane derivative of the amino acid may be synthesized as shownbelow in Scheme 2. As shown, 6-aminohexanoic acid is treated withformaldehyde in formic acid at reflux to give 6-(dimethylamino)hexanoicacid. The free carboxylic acid is then coupled to3-aminopropyl(trismethylsiloxy)silane in refluxing toluene to give thedesired siloxane derivative.

The N-terminal nitrogen may be further derivatized to modify or improvewater solubility and surface-active properties. A sample syntheticscheme is shown below in Scheme 3, in which the N-terminal nitrogen istreated with hydrochloric acid to give the corresponding hydrochloridesalt.

The N-terminal nitrogen may be alkylated. A sample synthetic scheme isshown below, in which the N-terminal nitrogen is treated with methyliodide to give the corresponding quaternary amine salt.

The N-terminal nitrogen may be treated with hydrogen peroxide in waterat reflux to give the corresponding N-oxide, as shown in the samplesynthetic scheme below, Scheme 5.

The compounds of the present disclosure demonstrate surface-activeproperties. These properties may be measured and described by variousmethods. One method by which surfactants may be described is by themolecule's critical micelle concentration (CMC). CMC may be defined asthe concentration of a surfactant at which micelles form, and abovewhich all additional surfactant is incorporated into micelles.

As surfactant concentration increases, surface tension decreases. Oncethe surface is completely overlaid with surfactant molecules, micellesbegin to form. This point represents the CMC, as well as the minimumsurface tension. Further addition of surfactant will not further affectthe surface tension. CMC may therefore be measured by observing thechange in surface tension as a function of surfactant concentration. Onesuch method for measuring this value is the Wilhemy plate method. AWilhelmy plate is usually a thin iridium-platinum plate attached to abalance by a wire and placed perpendicularly to the air-liquidinterface. The balance is used to measure the force exerted on the plateby wetting. This value is then used to calculate the surface tension (γ)according to Equation 1:

γ=F/I cos θ  Equation 1:

wherein I is equal to the wetted perimeter (2w+2d, in which w and d arethe plate thickness and width, respectively) and cos θ, the contactangle between the liquid and the plate, is assumed to be 0 in theabsence of an extant literature value.

Another parameter used to assess the performance of surfactants isdynamic surface tension. The dynamic surface tension is the value of thesurface tension for a particular surface or interface age. In the caseof liquids with added surfactants, this can differ from the equilibriumvalue. Immediately after a surface is produced, the surface tension isequal to that of the pure liquid. As described above, surfactants reducesurface tension; therefore, the surface tension drops until anequilibrium value is reached. The time required for equilibrium to bereached depends on the diffusion rate and the adsorption rate of thesurfactant.

One method by which dynamic surface tension is measured relies upon abubble pressure tensiometer. This device measures the maximum internalpressure of a gas bubble that is formed in a liquid by means of acapillary. The measured value corresponds to the surface tension at acertain surface age, the time from the start of the bubble formation tothe occurrence of the pressure maximum. The dependence of surfacetension on surface age can be measured by varying the speed at whichbubbles are produced.

Surface-active compounds may also be assessed by their wetting abilityon solid substrates as measured by the contact angle. When a liquiddroplet comes in contact with a solid surface in a third medium, such asair, a three-phase line forms among the liquid, the gas and the solid.The angle between the surface tension unit vector, acting at thethree-phase line and tangent at the liquid droplet, and the surface isdescribed as the contact angle. The contact angle (also known as wettingangle) is a measure of the wettability of a solid by a liquid. In thecase of complete wetting, the liquid is completely spread over the solidand the contact angle is 0°. Wetting properties are typically measuredfor a given compound at the concentration of 1-100×CMC, however, it isnot a property that is concentration-dependent therefore measurements ofwetting properties can be measured at concentrations that are higher orlower.

In one method, an optical contact angle goniometer may be used tomeasure the contact angle. This device uses a digital camera andsoftware to extract the contact angle by analyze the contour shape of asessile droplet of liquid on a surface.

Potential applications for the surface-active compounds of the presentdisclosure include formulations for use as shampoos, hair conditioners,detergents, spot-free rinsing solutions, floor and carpet cleaners,cleaning agents for graffiti removal, wetting agents for cropprotection, adjuvants for crop protection, and wetting agents foraerosol spray coatings.

It will be understood by one skilled in the art that small differencesbetween compounds may lead to substantially different surfactantproperties, such that different compounds may be used with differentsubstrates, in different applications.

The following non-limiting embodiments are provided to demonstrate thedifferent properties of the different surfactants. In Table 1 below,short names for the surfactants are correlated with their correspondingchemical structures.

TABLE 1 Surfactant Formula & Name Surfactant 1

6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide Surfactant 2

6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium chloride Surfactant 3

6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide Surfactant 4

6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-amine oxide Surfactant 5

4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate

Each of the five compounds are effective as surface-active agents,useful for wetting or foaming agents, dispersants, emulsifiers, anddetergents, among other applications.

Surfactants 1 and 2 candidates for use in a variety of surface cleaningand personal care product formulations as foaming or wetting agents.

Surfactant 3 is cationic. These surfactants are useful in both theapplications described above and some further special applications suchas surface treatments, such as in personal hair care products, and canalso be used to generate water repellant surfaces.

Surfactant 4 is non-ionic, and can be used in shampoos, detergents, hardsurface cleaners, and a variety of other surface cleaning formulations.

Surfactant 5 is zwitterionic. These surfactants are useful asco-surfactants in all of the applications described above.

The amount of the compounds disclosed herein used in a formulation maybe as low as about 0.001 wt. %, about 0.05 wt. %, about 0.1 wt. %, about0.5 wt. %, about 1 wt. %, about 2 wt. %, or about 5 wt. %, or as high asabout 8 wt. %, about 10 wt. %, about 15 wt. %, about 20 wt. %, or about25 wt. %, or within any range using any two of the foregoing values.

EXAMPLES

Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker500 MHz spectrometer. The critical micelle concentration (CMC) wasdetermined by the Wilhelmy plate method at 23° C. with a tensiometer(DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt—Ir plate.Dynamic surface tension was determined with a bubble pressuretensiometer (Kruss BP100, KrOss GmbH), at 23° C. Contact angle wasdetermined with the optical contact angle goniometer (OCA 15 Pro,DataPhysics GmbH) equipped with a digital camera.

Example 1a Synthesis of6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)ox)trisiloxan-3-yl)propyl)hexanamide(Surfactant 1) and6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propel)amino)-N,N-dimethyl-6-oxohexan-1-aminiumsalt (Surfactant 2)

6-(Dimethylamino)hexanoic acid (2.00 g, 12.56 mmol, 1 equiv.) wasdissolved in toluene (50 mL) in a 100 mL round bottom boiling flaskequipped with a Dean Stark trap, then3-aminopropyltris(trimethylsiloxy)silane (5.48 mL, 13.81 mmol, 1.1equiv.) was added. The reaction vessel was heated, and the reactionrefluxed for 24 hours until no more water separated in the Dean Starktube. The solvent was removed under vacuum to give Surfactant 1 as ayellow oil in 94% yield. ¹H NMR (500 MHz, DMSO) δ: 0.09 (s, 27H),0.28-0.31 (m, 2H), 1.12-1.26 (m, 2H), 1.27-1.30 (m, 4H), 1.38-1.41 (m,2H), 1.94 (t, J=7.3 Hz, 2H), 2.00 (s, 6H), 2.06-2.03 (m, 2H), 2.89 (dd,J=12.9, 6.8 Hz, 2H).

In its neutral form, Surfactant 1 is slightly soluble in pure waterwithout addition of hydrotropes or other surfactants, but afterprotonation in slightly acidic conditions it becomes interfaciallyactive (Surfactant 2). The acidic conditions can be generated by theaddition of any acid or acidic buffer in the pH range of 4-7. Surfactant2 can also be prepared in non-aqueous solutions, for example by sparginggaseous HCl in toluene in the presence of Surfactant 1.

Example 1b Determination of Critical Micelle Concentration (CMC) ofSurfactant 2

The critical micelle concentration (CMC) for Surfactant 2 was testedwith a chloride counterion and was determined to be about 2 mmol. Theplateau value of minimum surface tension that can be reached by thissurfactant is about 23 mN/m. FIG. 1 is a plot of these results, showingsurface tension versus concentration.

Example 2a Synthesis of6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexan-1-aminiumiodide (Surfactant 3)

Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv.) was dissolved in acetonitrile(10 mL) in a 100 mL round bottom flask. Next, Na₂CO₃ (0.26 g, 2.42 mmol,1.2 equiv.) was added and the mixture was stirred for 10 minutes. Methyliodide (0.377 mL, 6.06 mmol, 3 equiv.) was added and the reaction washeated at 40° C. for 24 hours. The cooled reaction mixture was filtered,and the solvent was removed under vacuum to give Surfactant 3 as aslightly yellow solid in quantitative yield. ⁻H NMR (500 MHz, DMSO) δ0.09 (s, 27H), 0.38-0.42 (m, 2H), 1.23-1.26 (m, 2H), 1.37-1.40 (m, 2H),1.52-1.55 (m, 2H), 1.65-1.69 (m, 2H), 2.08 (t, J=7.4 Hz, 2H), 2.99 (dd,J=13, 6.9 Hz, 2H), 3.04 (s, 9H),), 3.24-3.33 (m, 2H).

The pure product is soluble in water and has surfactant properties. Thehalogen anions may be directly obtained from the N-alkylation reaction,and other desired counter anions may be obtained by anion exchange.

Example 2b Determination of Physical Properties of Surfactant 3

The critical micelle concentration (CMC) for Surfactant 3 was measured.From the surface tension change with concentration in water, the CMC wasdetermined to be about 1.6 mmol. The plateau value of minimum surfacetension that can be reached by this surfactant is around 20 mN/m,indicating that the surfactant has outstanding interfacial activity.These results are plotted as surface tension versus concentration inFIG. 2.

The dynamic surface tension of Surfactant 3 was determined with a bubblepressure tensiometer which measures the change of surface tension of afreshly created air-water interface with time. FIG. 3 shows a plot ofthe results as surface tension versus time and demonstrates thatSurfactant 3 fully saturated the interface in less than 500 ms, makingit exceptionally fast in terms of interfacial adsorption.

In addition to Surfactant 3's ability to lower both interfacial andsurface tension, formulations containing only Surfactant haveexceptional wetting properties. For example, hydrophobic substrates suchas polyethylene and polypropylene exhibit a total surface wetting with acontact angle of 0°. On oleophobic and hydrophobic substrates such asTeflon, the measured contact angle was extremely low, 10.5° (Table 2).

TABLE 2 CA of Surfactant 3 CA of water Substrate (°) Concentration (°)Teflon 10.5 10× CMC 119 Polyethylene 0 10× CMC 91.5 Polypropylene 0 10×CMC 93.3 Nylon 0 10× CMC 50 Polyethylene terephthalate 0 10× CMC 65.3

Example 3a Synthesis of6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-amineoxide (Surfactant 4)

Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv.) was added to distilled water(80 mL) in a 100 mL round bottom flask, followed by 50% hydrogenperoxide (1.15 mL, 20.2 mmol, 10 equiv.). The reaction was refluxed for12 hours, then concentrated under vacuum. The residue was washed threetimes with acetone to give Surfactant 4 in 99% yield. ¹H NMR (500 MHz,DMSO) δ 0.09 (s, 27H), 0.38-0.44 (m, 2H), 1.21-1.25 (m, 2H), 1.35-1.42(m, 2H), 1.50-1.55 (m, 2H), 1.71-1.75 (m, 2H), 2.05-2.08 (m, 2H),2.97-3.00 (m, 2H), 3.01 (s, 9H), 3.11-3.14 (m, 2H).

Example 3b Determination of Physical Properties of Surfactant 4

The critical micelle concentration (CMC) for Surfactant 4 was measured.From the surface tension change with concentration in water, the CMC wasdetermined to be about 0.49 mmol. The plateau value of minimum surfacetension that can be reached by this surfactant is about 20 mN/m,indicating that the surfactant has outstanding interfacial activity.These results are plotted as surface tension versus concentration inFIG. 4.

The dynamic surface tension of Surfactant 4 was determined with a bubblepressure tensiometer. FIG. 5 shows a plot of the results as surfacetension versus time and demonstrates that Surfactant 4 fully saturated afreshly created air-water interface in one second or less, making itfast in terms of interfacial adsorption.

In addition to Surfactant 4's ability to lower both the interfacial andsurface tension, formulations containing only Surfactant 4 inconcentrations of 1-100×CMC have exceptional wetting properties. Forexample, a solution of Surfactant 4 in water at a concentration of10×CMC exhibits a 0° contact angle on hydrophobic substrates such aspolyethylene and polypropylene, and 10.6° on oleophobic and hydrophobicsubstrates such as Teflon. These contact angles are extremely low incomparison with the contact angle of water on the same substrate (Table3).

TABLE 3 CA of CA of water Substrate Surfactant 4 (°) Concentration (°)Teflon 10.6 10× CMC 119 Polyethylene 0 10× CMC 91.5 Polypropylene 0 10×CMC 93.3 Nylon 0 10× CMC 50 Polyethylene terephthalate 0 10× CMC 65.3

Example 4a Synthesis of4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate(Surfactant 5)

Surfactant 1(1.00 g, 2.02 mmol, 1 equiv.) was added to ethyl acetate(EtOAc) (30 mL) in a 100 mL round bottom flask, followed by 1,2-butanesultone (0.27 mL, 2.2 mmol, 1.1 equiv.). The reaction was refluxed for12 hours, after which the solvent was removed and the resultant whitewaxy solid was washed with acetone to give Surfactant 5 in 50% yield.¹HNMR (500 MHz, DMSO) δ 0.10 (s, 27H), 0.38-0.46 (m, 2H), 1.23-1.27 (m,2H), 1.37-1.68 (m, 10H), 1.73-1.78 (m, 2H), 2.45-2.48 (m, 2H), 2.97-3.01(m, 8H), 3.18-3.21 (m, 2H), 3.23-3.27 (m, 2H).

Example 4b Determination of Physical Properties of Surfactant 5

The critical micelle concentration (CMC) for Surfactant 5 was measured.From the surface tension change with concentration in water, the CMC wasdetermined to be about 0.39 mmol. The plateau value of minimum surfacetension that can be reached by this surfactant is about 21 mN/m,indicating that the surfactant has outstanding interfacial activity.These results are plotted as surface tension versus concentration inFIG. 6.

The dynamic surface tension of Surfactant 5 was determined with a bubblepressure tensiometer. FIG. 7 shows a plot of the results as surfacetension versus time and demonstrates that Surfactant 5 fully saturated afreshly created air-water interface in one second or less, making itfast in terms of interfacial adsorption.

Finally, a solution of Surfactant 5 in water at a concentration of10×CMC exhibits a 0° contact angle on hydrophobic substrates such aspolyethylene and polypropylene, and 10.2° on oleophobic and hydrophobicsubstrates such as Teflon. These contact angles are extremely low incomparison with the contact angle of water on the same substrate (Table4).

TABLE 4 CA of CA of water Substrate Surfactant 5 (°) Concentration (°)Teflon 10.2 10× CMC 119 Polyethylene 0 10× CMC 91.5 Polypropylene 0 10×CMC 93.3 Polyethylenterephthalate 0 10× CMC 65.3 Nylon 0 10× CMC 50Polyethylene-HD 0 10× CMC 93.6

Example 5 Formulation for Pesticides

In this Example, a concentrated formulation for use as a pesticide isprovided. The components of the formulation are shown below in Table 5.The formulation may also include additional surfactants, water,thickeners, deposition enhancers, drift control agents, and salts.

TABLE 5 Component Function Weight % Pesticide Agriculturally ActiveAgent   5-40 Surfactant Emulsifier  20-80 Water-Insoluble SolventSolvent 0.1-50

Example 6 Formulation for Liquid Fungicidal Composition

In this Example, a formulation for use as liquid fungicidal compositionis provided. The formulation is shown below in Table 6.

TABLE 6 Component Function Weight % Fungicide Agriculturally ActiveAgent 1-90 Surfactant Emulsifier 1-30 Co-Surfactant Co-Emulsifier 0-20Water-Insoluble Solvent Solvent 0-90

Example 7 Formulation for Herbicide

In this Example, a formulation for use as an herbicide is provided. Theformulation is shown below in Table 7.

TABLE 7 Component Function Weight % Herbicide Salt Agriculturally ActiveAgent   5-70 Second Herbicide Agriculturally Active Agent 0.1-40Surfactant Emulsifier   0-15 Water-Insoluble Solvent Solvent   0-50Water  20-80

Example 8 Formulation for Insecticide

In this Example, a formulation for use as an insecticide is provided.The formulation is shown below in Table 8.

TABLE 8 Component Function Weight % Insecticide Agriculturally ActiveAgent   5-70 Surfactant 0.1-40 Surfactant Anfifoaming Agent   0-15Thickener Viscosity Modifier   0-50 Water  20-80

ASPECTS

Aspect 1 is a formulation for a pesticide, comprising: at least onesurfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; and a pesticide.

Aspect 2 is the formulation of Aspect 1, further comprising awater-insoluble solvent.

Aspect 3 is the formulation of Aspect 1, wherein the pesticide is aninsecticide.

Aspect 4 is the formulation of Aspect 3, further comprising anantifoaming agent.

Aspect 5 is the formulation of Aspect 3 or Aspect 4, further comprisingan antifreezing agent.

Aspect 6 is the formulation of any of Aspects 3-5, further comprisingwater.

Aspect 7 is a formulation for a fungicide, comprising: at least onesurfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; and a fungicide.

Aspect 8 is the formulation of Aspect 7, further comprising aco-surfactant.

Aspect 9 is the formulation of either of Aspect 7 or Aspect 8, furthercomprising a carrier agent.

Aspect 10 is a formulation for an herbicide, comprising: at least onesurfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; and an herbicide.

Aspect 11 is the formulation of Aspect 10, further comprising a secondherbicide.

Aspect 12 is the formulation of either Aspect 10 or Aspect 11, furthercomprising a water-insoluble solvent.

Aspect 13 is the formulation of any of Aspects 10-12, further comprisingwater.

Aspect 14 is a formulation for an insecticide, comprising: at least onesurfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; and an insecticide.

Aspect 15 is the formulation of Aspect 14, further comprising anantifoaming agent.

Aspect 16 is the formulation of either of Aspect 14 or Aspect 15,further comprising an antifreezing agent.

Aspect 17 is the formulation of any of Aspects 14-16, further comprisingwater.

1. A formulation for a pesticide, comprising: at least one surfactant ofFormula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; and a pesticide.
 2. The formulation ofclaim 1, further comprising a water-insoluble solvent.
 3. Theformulation of claim 1, wherein the pesticide is an insecticide.
 4. Theformulation of claim 3, further comprising an antifoaming agent.
 5. Theformulation of claim 3, further comprising an antifreezing agent.
 6. Theformulation of claim 3, further comprising water.
 7. A formulation for afungicide, comprising: at least one surfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; and a fungicide.
 8. The formulation ofclaim 7, further comprising a co-surfactant.
 9. The formulation of claim7, further comprising a carrier agent.
 10. A formulation for anherbicide, comprising: at least one surfactant of Formula I,

wherein R¹ and R² may be the same or different, and comprise at leastone group selected from the group consisting of C₁-C₆ alkyl, optionallythe C₁-C₆ alkyl may include one or more of oxygen, nitrogen, or sulfuratoms or groups that include at least one of these atoms, and the alkylchain may be optionally substituted with one or more substituentsselected from the group consisting of hydroxyl, amino, amido, sulfonyl,sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1to 12; the terminal nitrogen is optionally further substituted with R³,wherein R³ is selected from the group consisting of hydrogen, oxygen,hydroxyl, and C₁-C₆ alkyl; an optional counterion associated with thecompound which, if present, is selected from the group consisting ofchloride, bromide, and iodide; and an herbicide.
 11. The formulation ofclaim 10, further comprising a second herbicide.
 12. The formulation ofclaim 10, further comprising a water-insoluble solvent.
 13. Theformulation of claim 10, further comprising water.